Process for making epoxides from ethylenic compounds with electron-with drawing groups



United States Patent Ofifice 3,313,829 Patented Apr. 11, 1967 The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment to us of any royalty thereon.

This is a division of Ser. No. 200,288, filed June 5, 1962, now US. Patent No. 3,183,250, issued May 11, 1965, entitled, Process for Making Epoxides From Ethylenic Compounds With Electron-Withdrawing Groups.

This invention relates to a novel process for making a new class of compounds designated by the formula Where X is H, F, Cl, or Br; R is CEN or CO-NH The compounds of the above formula are useful as monomers to prepare resins. For example, they can polymerize in the presence of acid catalysts to a hard infusible resin in a manner Well known in the art. The compound 2,2-dicyano-3-o-chlorophenyl oxirane has been found to be a strong vesicant, and therefore useful as a chemical Warfare agent.

The ethylenic starting materials for the herein described process are described in or can be made by the methods disclosed by Corson et al., Journal of the American Chemical Society, 50: 2825 (1928).

The process consists of reacting the ethylenic compounds corresponding to the final products with a hypochlorite ion generating material in an inert solvent at a pH in the range 3-9. Best results are obtained at a pH of 7. However, the reaction is operable in the broader range. The temperature range is not critical and can be from O-80 C.

For the purpose of this invention, we define a hypochlorite ion generating material as one which is capable of furnishing hypochlorite ions in an aqueous solution. Non-limiting examples of such materials are hypochlorous acid, sodium hypochlorite, lithium hypochlorite, calcium hypochlorite and neutral chlorine water.

The inert solvents which may be used are acetonitrile, water, dioxane, and tetrahydrofuran.

We have found that instead of obtaining a chlorohydrin as one would expect from the Work of Colonge, Bull. Soc. Chim. France 838-841 (1947) in which mesityl oxide was reacted with hypochlorous acid over a pH range of 4.5 to to obtain the corresponding chlorohydrin, one can obtain oxirane compounds from ethylenic compounds having strong electron-Withdrawing substitu ents. Thus, our process can be applied to olefins that are substituted by at least two strong electron-withdrawing groups. Examples of these possible starting materials are:

where AR is the phenyl radical or the phenyl radical substituted with halogen, nitro, cyano, carboxymethyl, acetyl, perchloryl o-r trialkylammonio radicals.

The reaction appears to follow the following scheme:

We carried out various experiments in order to define the role of the hypochlorite ion in this reaction. In the pH range where the hypochlorite ion-hypochlorous acid equilibrium is shifted predominantly to. the side of the latter species, the reaction rate which is constant at a given analytical concentration of hypochlorous acid increases proportionately to the increase in hydroxyl ion and hence proportionately with increasing hypochlorite ion concentration. At constant pH, within the same range as above, an increase in the analytical concentration of hypochlorous acid produces a proportional increase in the reaction rate constant.

These two pieces of experimental evidence, coupled with the fact that the reversal of the chlorohydrination reaction has never been reported and is highly improbable, leave the above postulated mechanism as the sole acceptable one for the present invention.

During the course of the reaction the pH is measured by a pH meter equipped with calomeland glass electrodes. The pH of the reaction mixture is measured periodically and when it remains approximately constant for one half hour, the reaction is considered to be complete.

Example 1 Solutions of 234 ml. of 0.141 molar aqueous hypochlorous acid and 47 ml. of 1 N sodium hydroxide are added concurrently to a solution of 5.66 grams of 1,1- dicyano-2-o-chlorophenyl ethylene in 270 ml. of acetonitrile, at such a rate as to maintain the pH of the mixture in the vicinity of 7. When the reaction is complete, as is evidenced by the pH remaining constant for one half hour, a little sodium chloride is added and the mixture is extracted with tWo portions of ether (250 and ml.). The combined ether extract is concentrated to remove all ether, leaving an oily residue, which is steam distilled. The oil collected in the steam distillate is crystallized from petroleum ether to give 2,2-dicyano-3-o-chlorophenyl oxirane, melting at 5152 C. and weighing 2.2 grams.

From the above examples it is evident that when the mole ratio of hypochlorite ion to olefine material is eq-uimolar the reaction proceeds only through to the epoxidation stage. With increasing amounts of hypochlorite ion, i.e., a molar excess, a cyano group is concurrently hydrolyzed to an amido group.

Example II Chlorine water is adjusted to pH 7 with sodium hydroxide to give a 0.121 M hypochlorite solution. A 225 ml. portion of this is added to a solution of 2.93 grams of 1,1dicyano2-o-chloropheny1 ethylene in 100 ml. of acetonitrile. The pH, measured by a portable pH meter, drops quickly to about 3 and is raised with about 14 ml. of 1 N sodium hydroxide, which, unless care is taken, may raise the pH to 11, in which case the pH is adjusted to 7 quickly with 0.1 N hydrochloric acid. The solvent is evaporated to dryness at reduced pressure and the residue is washed with ether, then with water, and then extracted with boiling ether. The extract is filtered and evaporated to dryness to give a solid residue which is recrystallized from benzene, yielding 0.43 gram of a compound, one of the isomers of Z-carboxamido-Z-cyano- 3-o-ch1orophenyl oxirane, which melts at 189190 C.

Calculated for C H O N Cl: C, 53.9; H, 3.17; O, 14.4. Found: C, 54.2; H, 3.2; O, 13.9.

From the above ether washings, by two fractional precipitations from benzene, followed by one recrystallization from chloroform-carbon tetrachloride and two recrystallizations from chloroform, 0.08 gram of second isomer of 2-carboxamido-2-cyano-3o-chlorophenyl oxirane is isolated, M.P. 138140 C. This was analyzed as C, 53.89; H, 3.2; O, 13.8.

We claim:

1. The method of producing a compound from the group of compounds represented by the formula,

H ON

4; wherein X is a member of the group consisting of hydrogen, fiuorine, chlorine and bromine, and R is a member of the group consisting of CN and CO-NH which comprises:

reacting in an inert solvent the compound,

H CN

wherein X is the same as above and R is CN with an amount of a hypochlorite ion-generating material sufficient to form said compound,

said reaction being conducted at a pH range of 3-9, and

recovering said compound with ether from the reaction solution.

2. A method of producing the compound 2,2-dicyano-. 3-o-chlorophenyl oxirane which comprises reacting one mole of 1,1dicyano2-o chlorophenyl-ethylene with one mole of hypochlorous acid in an excess of acetonitrile, maintaining the pH of the reaction near 7 by the periodic addition of base until the reaction is complete, extracting the product with ether and distilling the ether extract.

3. A method of producing 2-carboxamido-2-cyano-3- o-chlorophenyl oxirane which comprises adding two moles of sodium hypochlorite to one mole of 1,1-dicyano-2-ochlorophenyl ethylene dissolved in an excess of acetonitrile, maintaining the pH of the reaction near 7 by the addition of a member of the group consisting of acids and bases until the reaction is complete, extracting the product with ether, and recovering said product from the ether extract.

References Cited by the Examiner FOREIGN PATENTS 515,034 12/1930 Germany. 528,506 6/ 1931 Germany.

WALTER A. MODANCE, Primary Examiner.

NORMA S. MILESTONE, Assistant Examiner. 

1. THE METHOD OF PRODUCING A COMPOUND FROM THE GROUP OF COMPOUNDS REPRESENTED BY THE FORMULA 